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Lake Vida, located in Victoria Valley, is one of the largest lakes in the McMurdo dry valleys and is known to contain hypersaline liquid brine sealed below 16 m of freshwater ice. For the first time, Lake Vida was drilled to a depth of 27 m. Below 21 m the ice is marked by well-sorted sand layers up to 20 cm thick within a matrix of salty ice. From ice chemistry, isotopic composition of δ18O and δ2H, and ground penetrating radar profiles, we conclude that the entire 27 m of ice formed from surface runoff and the sediment layers represent the accumulation of surface deposits. Radiocarbon and optically stimulated luminescence dating limit the maximum age of the lower ice to 6300 14C yr BP. As the ice cover ablated downwards during periods of low surface inflow, progressive accumulation of sediment layers insulated and preserved the ice and brine beneath, analogous to the processes that preserve shallow ground ice. The repetition of these sediment layers reveals hydrologic variability in Victoria Valley during the mid- to late Holocene. Lake Vida is an exemplar site for understanding the preservation of subsurface brine, ice, and sediment in a cold desert environment.

The spatial distribution of organics in geological samples can be used to determine when and how these organics were incorporated into the host rock. Mass spectrometry (MS) imaging can rapidly collect a large amount of data, but ions produced are mixed without discrimination, resulting in complex mass spectra that can be difficult to interpret. Here, we apply unsupervised and supervised machine learning (ML) to help interpret spectra from time-of-flight-secondary ion mass spectrometry (ToF-SIMS) of an organic-carbon-rich mudstone of the Middle Jurassic of England (UK). It was previously shown that the presence of sterane molecular biomarkers in this sample can be detected via ToF-SIMS (Pasterski, M. J. et al., Astrobiology 2023, 23, 936). We use unsupervised ML on scanning electron microscopy-electron dispersive spectroscopy (SEM-EDS) measurements to define compositional categories based on differences in elemental abundances. We then test the ability of four ML algorithms─k-nearest neighbors (KNN), recursive partitioning and regressive trees (RPART), eXtreme gradient boost (XGBoost), and random forest (RF)─to classify the ToF-SIM spectra using (1) the categories assigned via SEM-EDS, (2) organic and inorganic labels assigned via SEM-EDS, and (3) the presence or absence of detectable steranes in ToF-SIMS spectra. In terms of predictive accuracy and balanced accuracy, KNN was the best performing model and RPART the worst. The feature importance, or the specific features of the ToF-SIM spectra used by the models to make classifications, cannot be determined for KNN, preventing posthoc model interpretation. Nevertheless, the feature importance extracted from the other models was useful for interpreting spectra. We determined that some of the organic ions used to classify biomarker containing spectra may be fragment ions derived from kerogen which is abundant in this mudstone sample.

Used crankcase oil is an important source of environmental polycyclic aromatic hydrocarbons (PAHs). Here, we use gas chromatography-mass spectrometry (GC-MS) to measure and compare the concentration of PAHs, including alkylated PAHs, in used oil against new and old oil stains and parking dust collected from a concrete, covered, open parking structure to understand the distribution of PAH in crankcase oil stains. PAH concentration in used oils ranges from 606 ng/mg to 1,592 ng/mg. The PAH distribution in used oil does not match that observed in parking oils stains, parking background, or parking dust. A comparison with PAH distributions in traffic related dusts extracted from the literature and dust collected from a neighboring open asphalt-paved parking suggests that covered parking dust includes substantial contributions from asphalt-paved parking dust, road dust, and/or coal tar dust. The parking dust is the most concentrated source of PAHs in the covered parking structure (PAHs up to 4,371 ng/mg), a small contribution of which can alter the distribution of PAHs in oil stains. Even with this contribution, we were able to observe a significant decrease of the ratio of low molecular weight PAHs to high molecular weight PAHs, and a significant increase in values of the phenanthrene/anthracene and fluoranthene/(fluoranthene + pyrene) ratios when oil stains age, suggesting biodegradation is an active attenuation process in covered, open parking structures., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors. Published by Elsevier Ltd.)

High hydrostatic pressure (HHP) is a key driver of life's evolution and diversification on Earth. Icy moons such as Titan, Europa, and Enceladus harbor potentially habitable high-pressure environments within their subsurface oceans. Titan, in particular, is modeled to have subsurface ocean pressures ≥ 150 MPa, which are above the highest pressures known to support life on Earth in natural ecosystems. Piezophiles are organisms that grow optimally at pressures higher than atmospheric (0.1 MPa) pressure and have specialized adaptations to the physical constraints of high-pressure environments - up to ~110 MPa at Challenger Deep, the highest pressure deep-sea habitat explored. While non-piezophilic microorganisms have been shown to survive short exposures at Titan relevant pressures, the mechanisms of their survival under such conditions remain largely unelucidated. To better understand these mechanisms, we have conducted a study of gene expression for Shewanella oneidensis MR-1 using a high-pressure experimental culturing system. MR-1 was subjected to short-term (15 min) and long-term (2 h) HHP of 158 MPa, a value consistent with pressures expected near the top of Titan's subsurface ocean. We show that MR-1 is metabolically active in situ at HHP and is capable of viable growth following 2 h exposure to 158 MPa, with minimal pressure training beforehand. We further find that MR-1 regulates 264 genes in response to short-term HHP, the majority of which are upregulated. Adaptations include upregulation of the genes argA, argB, argC , and argF involved in arginine biosynthesis and regulation of genes involved in membrane reconfiguration. MR-1 also utilizes stress response adaptations common to other environmental extremes such as genes encoding for the cold-shock protein CspG and antioxidant defense related genes. This study suggests Titan's ocean pressures may not limit life, as microorganisms could employ adaptations akin to those demonstrated by terrestrial organisms., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2024 Malas, Russo, Bollengier, Malaska, Lopes, Kenig and Meyer-Dombard.)

The ability to detect and map lipids, including potential lipid biomarkers, within a sedimentary matrix using mass spectrometry (MS) imaging may be critical to determine whether potential lipids detected in samples returned from Mars are indigenous to Mars or are contaminants. Here, we use gas chromatography-mass spectrometry (GC-MS) and time-of-flight-secondary ion mass spectrometry (ToF-SIMS) datasets collected from an organic-rich, thermally immature Jurassic geologic sample to constrain MS imaging analysis of indigenous lipid biomarkers in geologic samples. GC-MS data show that the extractable fractions are dominated by C 27 -C 30 steranes and sterenes as well as isorenieratene derivatives. ToF-SIMS spectra from organic matter-rich laminae contain a strong, spatially restricted signal for ions m/z 370.3, m/z 372.3, and m/z 386.3, which we assign to C 27 sterenes, cholestane (C 27 ), and 4- or 24-methyl steranes (C 28 ), respectively, as well as characteristic fragment ions of isorenieratene derivatives, including m/z 133.1, m/z 171.1, and m/z 237.1. We observed individual steroid spatial heterogeneity at the scale of tens to hundreds of microns. The fine-scale heterogeneity observed implies that indigenous lipid biomarkers concentrated within specific regions may be detectable via ToF-SIMS in samples with even low amounts of organic carbon, including in samples returned from Mars.

The study of lipid molecular fossils by traditional biomarker analysis requires bulk sample crushing, followed by solvent extraction, and then the analysis of the extract by gas chromatography-mass spectrometry (GC-MS). This traditional analysis mixes all organic compounds in the sample regardless of their origins, with a loss of information on the spatial distribution of organic molecules within the sample. These shortcomings can be overcome using the chemical mapping of intact samples. Spectroscopic techniques such as UV fluorescence or Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are among those elemental and molecular mapping techniques. This study employed femtosecond (fs) laser ablation combined with single-photon ionization, a method called fs-laser desorption postionization mass spectrometry (fs-LDPI-MS). A pulsed ∼75 fs, 800 nm laser was used to ablate the geological sample, which was then photoionized after a few microseconds by a pulsed 7.9 eV vacuum ultraviolet laser. An organic carbon-rich geological sample was used for this study to map hydrocarbon biomarkers in sediments that were previously studied by GC-MS. The petrography of this sample was examined by optical and fluorescence microscopy. It is demonstrated here that fs-LDPI-MS combined with petrography for multimodal imaging can expose buried compounds within the sample via in situ layer removal. When used in conjunction with traditional organic geochemical analysis, this method has the potential to determine the spatial distribution of organic biomarkers in geological material. Finally, fs-LDPI-MS imaging data are compared with ToF-SIMS imaging that is commonly used for such studies.

The period 800-717 million years (Ma) ago, in the lead-up to the Sturtian Snowball glaciation, saw an increase in the diversity of eukaryotic microfossils. To afford an independent and complementary view of this evolutionary period, this study presents the distribution of eukaryotic biomarkers from three pre-Sturtian successions across the supercontinent Rodinia: the ca. 780 Ma Kanpa Formation of the Western Australian Officer Basin, the ca. 800-740 Ma Visingsö Group of Sweden, and the 740 Ma Chuar Group in Arizona, USA. The distribution of eukaryotic steranes is remarkably similar in the three successions but distinct from all other known younger and older sterane assemblages. Cholestane was the only conventional structure, while indigenous steranes alkylated in position C-24, such as ergostane, stigmastane, dinosterane and isopropylcholestane, and n-propylcholestane, were not observed. This sterane distribution appears to be age diagnostic for the pre-Sturtian Neoproterozoic. It attests to the distinct evolutionary state of pre-Snowball eukaryotes, pointing to a taxonomic disparity that was still lower than in the Ediacaran (635-541 Ma). All three basins also show the presence of a new C28 sterane that was tentatively identified as 26-methylcholestane, here named cryostane. The only known extant organisms that can methylate sterols in the 26-position are demosponges. This assignment is plausible as molecular clocks place the appearance of the earliest animals into the pre-Sturtian Neoproterozoic. The unusual 26-methylsterol may have protected sponges, but also other eukaryotes, against their own membranolytic toxins. Some protists release lytic toxins to deter predators and kill eukaryotic prey. As conventional membrane sterols can be the site of attack for these toxins, sterols with unusual side-chain modification protect the cell. This interpretation of cryostane supports fossil evidence of predation in the Chuar Group and promotes hypotheses about the proliferation of eukaryophagy in the lead-up to the Cryogenian., (© 2015 John Wiley & Sons Ltd.)

The permanent ice cover of Lake Vida (Antarctica) encapsulates an extreme cryogenic brine ecosystem (-13 °C; salinity, 200). This aphotic ecosystem is anoxic and consists of a slightly acidic (pH 6.2) sodium chloride-dominated brine. Expeditions in 2005 and 2010 were conducted to investigate the biogeochemistry of Lake Vida's brine system. A phylogenetically diverse and metabolically active Bacteria dominated microbial assemblage was observed in the brine. These bacteria live under very high levels of reduced metals, ammonia, molecular hydrogen (H(2)), and dissolved organic carbon, as well as high concentrations of oxidized species of nitrogen (i.e., supersaturated nitrous oxide and ∼1 mmol⋅L(-1) nitrate) and sulfur (as sulfate). The existence of this system, with active biota, and a suite of reduced as well as oxidized compounds, is unusual given the millennial scale of its isolation from external sources of energy. The geochemistry of the brine suggests that abiotic brine-rock reactions may occur in this system and that the rich sources of dissolved electron acceptors prevent sulfate reduction and methanogenesis from being energetically favorable. The discovery of this ecosystem and the in situ biotic and abiotic processes occurring at low temperature provides a tractable system to study habitability of isolated terrestrial cryoenvironments (e.g., permafrost cryopegs and subglacial ecosystems), and is a potential analog for habitats on other icy worlds where water-rock reactions may cooccur with saline deposits and subsurface oceans.

The biopolymer sporopollenin present in the spore/pollen walls of all land plants is regarded as one of the most recalcitrant biomacromolecules (biopolymers), providing protection against a range of abiotic stresses. This long-term stability is demonstrated by the near-ubiquitous presence of pollen and spores in the fossil record with spores providing the first evidence for the colonization of the land. Here, we report for the first time chemical analyses of geologically unaltered sporopollenin from Pennsylvanian (c. 310 million yr before present (MyBP)) cave deposits. Our data show that Pennsylvanian Lycophyta megaspore sporopollenin has a strong chemical resemblance to extant relatives and indicates that a co-polymer model of sporopollenin formation is the most likely configuration. Broader comparison indicates that extant sporopollenin structure is similar across widely spaced phylogenetic groups and suggests land plant sporopollenin structure has remained stable since embryophytes invaded land., (© 2012 The Authors. New Phytologist © 2012 New Phytologist Trust.)

A helicopter crashed in January 2003 on the 5 m-thick perennial ice cover of Lake Fryxell, spilling synthetic turbine oil Aeroshell 500. Molecular compositions of the oils were analyzed by gas chromatography-mass spectrometry and compared to the composition of contaminants in ice, meltwater, and sediments collected a year after the accident. Aeroshell 500 is based on C20-C33 Pentaerythritol triesters (PET) with C5-C10 fatty acids susbstituents and contain a number of antioxidant additives, such as tricresyl phosphates. Biodegradation of this oil in the ice cover occurs when sediments are present PETs with short fatty acids substituents are preferentially degraded, whereas long chain fatty acids seem to hinder esters from hydrolysis by esterase derived from the microbial assemblage. It remains to be seen if the microbial ecosystem can degrade tricresyl phosphates. These more recalcitrant PET species and tricresyl phosphates are likely to persist and comprise the contaminants that may eventually cross the ice cover to reach the pristine lake water.

In January 2003, a helicopter crashed on the 5 m thick perennial ice cover of Lake Fryxell (McMurdo Dry Valleys, East Antarctica), spilling approximately 730 l of aviation diesel fuel (JP5-AN8 mixture). The molecular composition of the initial fuel was analyzed by solid phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS), then compared to the composition of the contaminated ice, water, and sediments collected a year after the spill. Evaporation is the major agent of diesel weathering in meltpool waters and in the ice. This process is facilitated by the light non-aqueous phase liquid properties of the aviation diesel and by the net upward movement of the ice as a result of ablation. In contrast, in sediment-bearing ice, biodegradation by both alkane- and aromatic-degraders was the prominent attenuation mechanism. The composition of the diesel contaminant in the ice was also affected by the differential solubility of its constituents, some ice containing water-washed diesel and some ice containing exclusively relatively soluble low molecular weight aromatic hydrocarbons such as alkylbenzene and naphthalene homologues. The extent of evaporation, water washing and biodegradation between sites and at different depths in the ice are evaluated on the basis of molecular ratios and the results of JP5-AN8 diesel evaporation experiment at 4 degrees C. Immediate spread of the aviation diesel was enhanced where the presence of aeolian sediments induced formations of meltpools. However, in absence of melt pools, slow spreading of the diesel is possible through the porous ice and the ice cover aquifer.

Highly cracked and isomerized archaeal lipids and bacterial lipids, structurally changed by thermal stress, are present in solvent extracts of 2,707- to 2,685-million-year-old (Ma) metasedimentary rocks from Timmins, ON, Canada. These lipids appear in conventional gas chromatograms as unresolved complex mixtures and include cyclic and acyclic biphytanes, C36-C39 derivatives of the biphytanes, and C31-C35 extended hopanes. Biphytane and extended hopanes are also found in high-pressure catalytic hydrogenation products released from solvent-extracted sediments, indicating that archaea and bacteria were present in Late Archean sedimentary environments. Postdepositional, hydrothermal gold mineralization and graphite precipitation occurred before metamorphism (approximately 2,665 Ma). Late Archean metamorphism significantly reduced the kerogen's adsorptive capacity and severely restricted sediment porosity, limiting the potential for post-Archean additions of organic matter to the samples. Argillites exposed to hydrothermal gold mineralization have disproportionately high concentrations of extractable archaeal and bacterial lipids relative to what is releasable from their respective high-pressure catalytic hydrogenation product and what is observed for argillites deposited away from these hydrothermal settings. The addition of these lipids to the sediments likely results from a Late Archean subsurface hydrothermal biosphere of archaea and bacteria.

With a view to the authentication of an unusual series of branched alkanes with quaternary centers (BAQCs) isolated from geological samples, and whose structures rest on the interpretation of EI-mass spectral fragmentation patterns, the total synthesis of 3-ethyl-3-methylheptadecane, 3,3-dimethylheptadecane, 3,3,11,11-tetraethyltridecane, and 5,5,7,7-tetraethylundecane is described. The GC-MS data of the first two samples are identical with those of the isolates and confirm their structures. However, the GC-MS data of the two more highly branched structures do not match those of the geological isolates leading to the conclusion that these structures were erroneously assigned.

A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65 degrees C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers.

Little is known about the potential for life in the vast, low-temperature (<100 degrees C) reservoir of fluids within mid-ocean ridge flank and ocean basin crust. Recently, an overpressured 300-meter-deep borehole was fitted with an experimental seal (CORK) delivering crustal fluids to the sea floor for discrete and large-volume sampling and characterization. Results demonstrate that the 65 degrees C fluids from 3.5-million-year-old ocean crust support microbial growth. Ribosomal RNA gene sequence data indicate the presence of diverse Bacteria and Archaea, including gene clones of varying degrees of relatedness to known nitrate reducers (with ammonia production), thermophilic sulfate reducers, and thermophilic fermentative heterotrophs, all consistent with fluid chemistry.

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.

A new route for the formation of gammacerane from tetrahymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids. Selective cleavage of polysulphide linkages with MeLi/MeI led to formation of 3-methylthiogammacerane, indicating that the gammacerane skeleton is primarily bound via sulphur at position 3, consistent with the idea that tetrahymanol (or the corresponding ketone) is the precursor for gammacerane. Second, upon mild artificial maturation of two sediments using hydrous pyrolysis, gammacerane is released from S-rich macromolecular aggregates by cleavage of the relatively weak C-S bonds. The stable carbon isotopic compositions of gammacerane and lipids derived from primary producers and green sulphur bacteria in both the Miocene Gessoso-solfifera and Upper Jurassic Allgau Formations indicate that gammacerane is derived from bacterivorous ciliates which were partially feeding on green sulphur bacteria. This demonstrates that anaerobic ciliates living at or below the chemocline are important sources for gammacerane, consistent with the fact that ciliates only biosynthesize tetrahymanol if their diet is deprived of sterols. This leads to the conclusion that gammacerane is an indicator for water column stratification, which solves two current enigmas in gammacerane geochemistry. Firstly, it explains why gammacerane is often found in sediments deposited under hypersaline conditions but is not necessarily restricted to this type of deposits. Secondly, it explains why lacustrine deposits may contain abundant gammacerane since most lakes in the temperate climatic zones are stratified during summer.

A total of 165 samples was obtained from the Oxford Clay Formation at seven different sites. Nearly all were from the Peterborough Member (Lower Oxford Clay), but seven were from the Stewartby and Weymouth Members (Middle and Upper Oxford Clay respectively). Five samples from the underlying Kellaways Formation were also examined. Stratigraphic relationships were estimated on the basis of ammonite subzones and results from all locations can be placed along a single stratigraphic scale. The following were determined for all samples: abundance and isotopic composition of organic carbon, abundances of carbonate carbon and total sulphur, and the Rock-Eval pyrolysis parameters hydrogen index, oxygen index and Tmax. For a subset of eight samples selected to be representative of geochemical and apparent palaeoenvironmental variations, soluble organic compounds were extracted and the isotopic composition of pristane, phytane, and long-chain n-alkanes determined by isotope-ratio-monitoring gas chromatograph mass spectrometry. Concentrations of organic carbon in samples from the Peterborough Member ranged from 0.5 to 16.6 % and delta values of total organic carbon (TOC) ranged from -27.7 to -23.1% v. PDB. Shales dominated by epifaunal bivalve assemblages have high concentrations of TOC and values of H index approaching 800, indicating preservation of hydrogen-rich organic material. Conversely, shell beds and calcareous and silty clay beds have lower abundances of TOC and values of H index dropping below 100, indicating extensive oxidation of the organic matter. Isotopic composition of pristane and phytane in the Peterborough and Stewartby Members average -31.7%, those in the Weymouth Member average -29.8. Values of delta for long-chain n-alkanes average -28%. Together these results indicate delta values for primary inputs as follows: terrestrial vascular plants, -23.5%; Peterborough Member algae, -28.2; Stewartby Member algae, -29.1%; Weymouth Member algae, -26.6% Comparison of primary delta values to those of TOC indicates that in some cases secondary processes enriched TOC relative to primary inputs by as much as 4%. Paleontological evidence in these same beds indicates development of extensive food-webs and supports attribution of this isotopic enrichment to heterotrophic reworking.